KR101801048B1 - Indolocarbazole derivatives and organoelectroluminescent device using the same - Google Patents

Abstract

상기 [화학식 1]에서 A 및 n은 발명의 상세한 설명에 기재된 바와 같다.The present invention relates to an indolocarbazole derivative represented by the following formula (1) and an organic electroluminescent device comprising the same. The organic electroluminescent device comprising the indolocarbazole derivative according to the present invention has a low driving voltage The efficiency is excellent.
[Chemical Formula 1]

A and n in the above formula (1) are as described in the description of the invention.

Description

[Technical Field] The present invention relates to indolocarbazole derivatives, and to organic electroluminescent devices using the same. BACKGROUND ART [0002] Indolocarbazole derivatives and organoelectroluminescent devices using the same

TECHNICAL FIELD The present invention relates to an aromatic compound and an organic electroluminescent device using the same. More particularly, the present invention relates to an indolocarbazole derivative and an organic electroluminescent device using the same and having a low driving voltage and excellent luminous efficiency.

Organic electroluminescent devices have been increasingly applied to display and illumination fields of various electronic products. However, efficiency and lifetime characteristics are limiting the expansion of application fields. In order to improve efficiency and lifetime characteristics, Many studies are under way. A host-dopant system is mainly adopted as a method for maximizing luminous efficiency from the viewpoint of materials, a phosphorescent dopant as a light emitting material, and a host capable of maximizing the luminescent characteristics of a dopant include CBP (4, 4'-N, N'-dicarbazolbipheny) and carbazole (JP-A-2008-0214244 and JP-A-2003-0133075), but further improvement is required in terms of efficiency and life span.

A first object of the present invention is to provide a novel indolocarbazole derivative having a low driving voltage and a high luminous efficiency of an organic electroluminescent device.

Another object of the present invention is to provide an organic electroluminescent device improved in characteristics by employing the indolocarbazole derivative.

In order to accomplish the first object, the present invention provides indolecarbazole derivatives of the following formula (1).

[Chemical Formula 1]

In the above formula (1), n is an integer of 1 to 5,

When n is 1, A is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms containing at least one nitrogen,

When n is 2 or more, each A may independently be the same or different and is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, And a heteroaryl group having 3 to 40 carbon atoms, wherein at least one heteroaryl group containing at least one nitrogen must be contained,

The substituent of A may be a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, An aryloxy group having 3 to 40 carbon atoms, an arylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, Or a heteroaryl group having 1 to 40 carbon atoms.

According to an embodiment of the present invention, when n is 2 or more, the A may be bonded to each other to form a ring having a saturated or unsaturated ring or a hetero atom. The substituents of A may be bonded to each other to form a saturated or unsaturated ring, or may be fused together by a pendant method.

According to another embodiment of the present invention, the indolocarbazole derivative may be any one selected from the group consisting of the following chemical formulas [SPH01] to [SPH99] It is not.

[SPH01] [SPH02] [SPH03]

[SPH04] [SPH05] [SPH06]

[SPH07] [SPH08] [SPH09]

[SPH10] [SPH11] [SPH12]

[SPH13] [SPH14] [SPH15]

[SPH16] [SPH17] [SPH18]

[SPH19] [SPH20] [SPH21]

[SPH22] [SPH23] [SPH24]

[SPH25] [SPH26] [SPH27]

[SPH28] [SPH29] [SPH30]

[SPH31] [SPH32] [SPH33]

[SPH34] [SPH35] [SPH36]

[SPH37] [SPH38] [SPH39]

[SPH40] [SPH41] [SPH42]

[SPH43] [SPH44] [SPH45]

[SPH46] [SPH47] [SPH48]

[SPH49] [SPH50] [SPH51]

[SPH52] [SPH53] [SPH54]

[SPH55] [SPH56] [SPH57]

[SPH58] [SPH59] [SPH60]

[SPH61] [SPH62] [SPH63]

[SPH64] [SPH65] [SPH66]

[SPH67] [SPH68] [SPH69]

[SPH70] [SPH71] [SPH72]

[SPH73] [SPH74] [SPH75]

[SPH76] [SPH77] [SPH78]

[SPH79] [SPH80] [SPH81]

[SPH82] [SPH83] [SPH84]

[SPH85] [SPH86] [SPH87]

[SPH88] [SPH89] [SPH90]

[SPH91] [SPH92] [SPH93]

[SPH94] [SPH95] [SPH96]

[SPH97] [SPH98] [SPH99]

The present invention, in order to achieve the second technical object, Cathode; And a layer comprising an indolocarbazole derivative represented by the formula (1) interposed between the anode and the cathode.

According to an embodiment of the present invention, at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode And the indolocarbazole derivative is contained in the light emitting layer between the anode and the cathode, and the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM.

The use of the indolocarbazole derivative according to the present invention can provide an organic electroluminescent device having a low driving voltage and an excellent luminous efficiency.

1A to 1F are cross-sectional views illustrating a stacked structure of organic electroluminescent devices according to a preferred embodiment of the present invention.

The present invention relates to indolecarbazole derivatives represented by the above formula (1), which can be effectively used in all layers of organic electroluminescent devices. In particular, when used as a light emitting layer host, It is possible to maximize the formation of excitons in the light emitting layer.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. A substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R (in this case, ''), R 'and R "are independently an alkyl group having 1 to 10 carbon atoms, and in this case, they are referred to as" alkylamino group "), hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, , A halogenated alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, A heteroaryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms Lt; / RTI > alkyl group.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, hexyloxy, At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as the alkyl group.

The aryl group used in the compounds of the present invention means an aromatic system comprising at least one ring, which rings may be attached together or fused together by a pendant method. The aryl group also includes a non-condensed aromatic group. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, chrysenyl and fluoranthenyl, and examples of the non-condensed aromatic group include biphenyl, .

At least one hydrogen atom of the aryl group may be substituted with the same substituent as the alkyl group (for example, an "arylamino group" when it is substituted with an amino group, an "arylsilyl group" when it is substituted with a silyl group, Quot; aryloxy group "when it is substituted with a group).

The heteroaryl group which is a substituent used in the compound of the present invention means a ring aromatic system having 3 to 30 carbon atoms in which the remaining ring atoms are carbon atoms containing 1, 2 or 3 hetero atoms selected from N, O or S, Can be attached together in a pendant manner. When the heteroaryl group is fused with an aryl group or other heteroaryl group, it is referred to as a condensed aromatic heterocycle.

Specific examples of the heteroaryl group include a pyrrolyl group, a furane group, a thiophene group, a bithiophene group, a thiophene group, a pyrazole group, an imidazole group, a triazole group, an isoxazole group, an oxazole group, an oxadiazole group, A pyridyl group, a terpyridine group, a pyridazine group, a pyrimidine group, a pyrazine group, and a triazine group.

Specific examples of the condensed aromatic heterocyclic group include an indole group, a carbazole group, a dibenzoazepin group, an azo group, an indolocarbazole group, a benzofuran group, a dibenzofurane group, a thianaphthene group, a dibenzothiophen group, A benzothiazole group, a benzothiadiazole group, a triazolopyrimidine group, a purine group, a quinoline group, a benzoquinoline group, an acridine group, an isoquinoline group, an imidazolidine group, A phenanthroline group, a phthalazine group, a quinazoline group, a phenoxaline group, a phenanthrene group, a phenanthroline group, a phenoxazine group and the like.

And at least one hydrogen atom of the heteroaryl group and the condensed aromatic heterocycle may be substituted with the same substituent as the alkyl group.

According to another aspect of the present invention, there is provided a plasma display panel comprising: an anode; Cathode; And a layer comprising an indolocarbazole derivative represented by the formula (1) interposed between the anode and the cathode.

The organic electroluminescent device according to the present invention may further include at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer between the anode and the cathode The hole injecting layer, the hole transporting layer, the electron transporting layer, and the electron injecting layer efficiently transport holes or electrons to the light emitting layer, thereby enhancing the probability of light emitting coupling in the light emitting layer.

The hole injecting layer and the hole transporting layer are laminated in order to inject holes from the anode and transport the injected holes. As the material for the hole transporting layer, electron donating molecules having a small ionization potential are used. Diamine, triamine or tetraamine derivatives having an amine as a basic skeleton are widely used.

In the present invention, as the material of the hole transport layer, various materials can be used without limitation as long as they are commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine (? -NPD ) Can be used.

In addition, a HIL (Hole Injection Layer) may be additionally deposited on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, CuPc or starburst type amines such as TCTA, m-MTDATA, and IDE406 (manufactured by Idemitsu) can be used.

        [CuPc] [TCTA]

       [m-MTDATA]

An organic light emitting layer is laminated on the hole transport layer. The organic light emitting layer may be formed of a single material or a host / dopant.

In general, when such a compound is used as a single substance, a host / dopant luminescent layer is preferable because a mound peak in a long wavelength is generated due to intermolecular interaction, the color purity drops, The indolocarbazole derivative may be used as a host material in a host / dopant emitting layer.

In general, CBP (4,4'-dicarbazolyl-1,1'-biphenyl) is used as a host material in the host / dopant emission layer and Ir (ppy) 3 is used as a dopant material. Is not particularly limited as long as it is used as the "

The electron transporting layer serves to smoothly transport electrons supplied from the cathode to the light emitting layer and to suppress the movement of holes that are not coupled in the light emitting layer, thereby increasing the chance of recombination in the light emitting layer.

The material of the electron transport layer is not particularly limited as long as it is a material used in the art, and examples thereof include Alq3 (tri-8-hydroxyquinoline aluminum), PBD (2- (4- 4-t-butylphenyl) -1,3,4-oxadiazole), TNF (2,4,7-trinitrofluorenone), BMD, BND and the like.

On the other hand, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. May be used without any particular limitation as long as it is commonly used in the art. For example, materials such as LiF, NaCl, CsF, Li2O, and BaO may be used.

Furthermore, the organic electroluminescent device according to the present invention may further include additional functional laminated structures such as a hole blocking layer or an electron blocking layer in addition to the above-mentioned hole injecting layer, hole transporting layer, electron transporting layer and electron injecting layer . In this case, when the holes are injected into the cathode through the organic light emitting layer, the hole blocking layer reduces the lifetime and the efficiency of the device. Therefore, the use of a material having a very low HOMO level prevents the problem. The material forming the hole blocking layer is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having an electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

1A to 1F illustrate organic electroluminescent devices having various laminated structures. Referring to FIG. 1A, the organic electroluminescent device of FIG. 1A includes an anode, a hole injection layer, a light emitting layer, and a cathode And the organic electroluminescent device of FIG. 1B has a structure composed of an anode / a hole injection layer / a light emitting layer / an electron injection layer / a cathode.

1C has the structure of anode / hole injection layer / hole transporting layer / light emitting layer / cathode, and the organic electroluminescent element shown in FIG. 1D has an anode / hole injection layer / hole transporting layer / light emitting layer / electron injection 1E has a structure of anode / hole injection layer / hole transporting layer / light emitting layer / electron transporting layer / electron injecting layer / cathode, and finally the organic electroluminescent device of FIG. / Hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode structure.

The organic electroluminescent device according to the present invention may comprise the indolocarbazole derivative in various laminated structures interposed between the anode and the cathode, but preferably the indolocarbazole derivative has a structure in which the light-emitting layer between the anode and the cathode Can be used as a host material.

In addition, the thickness of the light emitting layer including the indolocarbazole derivative may be 50 to 2,000 ANGSTROM. If the thickness is less than 50 ANGSTROM, the luminous efficiency is decreased. If the thickness is more than 2,000 ANGSTROM, It is economical.

A method of manufacturing an organic electroluminescent device according to the present invention will be described with reference to Figs. 1A to 1F.

First, the anode material is coated on the substrate. As the substrate, a substrate used in a conventional light emitting device is used, and a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode material, materials commonly used in the art such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2) or zinc oxide (ZnO) which are transparent and excellent in conductivity can be used . A hole injection layer is stacked on the anode, and then a hole transport layer is formed on the hole injection layer.

Next, a light emitting layer is laminated on the hole transporting layer, and a hole blocking layer is selectively formed thereon. Finally, an organic electroluminescent device according to the present invention can be manufactured by selectively forming an electron injecting layer after laminating an electron transporting layer on the hole blocking layer, and vacuum depositing a cathode forming metal on the electron injecting layer . The lamination of the organic layers is performed by one or more methods selected from the methods of vacuum thermal deposition, spin coating or ink jet printing.

On the other hand, examples of the cathode forming metal include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium- Magnesium-silver (Mg-Ag) or the like may be used. In order to obtain a top-emitting device, a transmissive cathode using ITO or IZO may be used.

<Examples>

Synthesis Example 1 Synthesis of a compound represented by [SPH10]

(1) Synthesis of Compound Represented by Formula (1-a)

[Chemical Formula 1-a] was synthesized by the following Reaction Scheme 1.

[Reaction Scheme 1]

                                                       [Chemical Formula 1-a]

50 g (0.45 mol) of 1,2-cyclohexanedione, 135 g (0.92 mol) of phenylhydrazine-hydrochloride and 1500 ml of ethyl alcohol were placed in a 2 L round bottom flask, and after stirring for 30 minutes, 5 ml is added. Stir at 65 占 폚 for 10 hours. When the reaction is completed, the reaction mixture is cooled to room temperature, filtered and washed with ethyl alcohol.

The filtrate was filtered through a 2 L round-bottom flask, 1200 ml of acetic acid and 120 ml of trifluoroacetic acid were added to the filtrate without refining at room temperature, and the mixture was stirred at 110 ° C for 8 hours. When the reaction is completed, the reaction mixture is cooled to room temperature, filtered, and washed with ethyl alcohol and hexane. And dried under reduced pressure at room temperature to obtain 80 g of a compound represented by the general formula [1-a]. (Yield: 76.8%)

(2) Synthesis of Compound Represented by Formula (1-b)

[Chemical Formula 1-b] was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

          [Chemical Formula 1-a] [Chemical Formula 1-b]

48.5 g (0.189 mol) of the compound represented by the formula (I-a), 42.5 g (0.208 mol) of iodobenzene, 19.4 g (0.378 mol) of copper powder, 15 g (0.057 mol) of potassium carbonate and 104.5 g (0.756 mol) of potassium carbonate are added in this order, and 480 ml of ortho-dichlorobenzene is added thereto, followed by reflux at 180 ° C for 2 days.

When the reaction is complete, extract using 500 ml of methylene chloride and 400 ml of distilled water. Repeat 2 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane alone to remove the ortho-dichlorobenzene. After the solvent was removed, methylene chloride was added in an excessive amount to obtain an impure product, which was subjected to column chromatography using methylene chloride: hexane = 1: 10 to obtain 17.9 g of a compound represented by the formula (1-b). (Yield: 28%)

(3) Synthesis of Compound Represented by Formula (1-c)

[Chemical Formula 1-c] was synthesized by the following Reaction Scheme 3.

[Reaction Scheme 3]

             [Chemical Formula 1-b] [Chemical Formula 1-c]

27.7 g (0.083 mol) of the compound represented by the formula 1-c, 39.1 g (0.108 mol) of 1,3-dibromo-5-iodobenzene and 15.8 g (0.249 mol) of the copper powder were added to a 1 L round- 4.4 g (0.017 mol) of 18-crown-6 and 57.48 g (0.415 mol) of potassium carbonate were added in this order, 270 ml of ortho-dichlorobenzene was added thereto, and the mixture was refluxed at 180 ° C for 3 days.

When the reaction is complete, extract using 200 ml of methylene chloride and 200 ml of distilled water. Repeat 2 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane alone to remove the ortho-dichlorobenzene. After the solvent was removed, methylene chloride was added in an excessive amount to obtain an impure product, which was then subjected to column chromatography with methylene chloride: hexane = 1: 20 to obtain 30 g of a compound represented by the formula (1-c). (Yield 64%)

(4) Synthesis of a compound represented by the formula (1-d)

[Chemical Formula 1-d] was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

           [Chemical Formula 1-c] [Chemical Formula 1-d]

(0.0032 mol) of PdCl2 (dppf), 32.4 g (0.126 mol) of bis (pinacolato) diboron, 29.4 g (0.052 mol) of the compound represented by the formula (1-c) in a 1000 mL round bottom flask, 23.6 g (0.312 mol) of potassium acetate and 500 ml of dimethylsulfoxide were added, and the mixture was refluxed at 110 DEG C for 1 day.

When the reaction is complete, extract using 200 ml of methylene chloride and 200 ml of distilled water. Repeat 3 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using methylene chloride: hexane = 1: 20 to obtain 26.7 g of a compound represented by the formula (1-d). (Yield: 78%)

(5) Synthesis of compound represented by [SPH10]

[SPH10] was synthesized according to Reaction Scheme 5 below.

[Reaction Scheme 5]

           [Formula 1-d] [SPH10]

15 g (0.024 mol) of the compound represented by the formula [1-d], 16 g (0.06 mol) of chlorodiphenylamine, 0.7 g (0.0006 mol) of Pd [PPh3] g (0.0588 mol), tetrahydrofuran (50 ml), toluene (50 ml) and water (20 ml), and the mixture was refluxed at 80 ° C for 5 hours.

When the reaction is complete, extract using 50 ml of ethyl acetate and 100 ml of distilled water. Repeat 2 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized with methylene chloride and hexane to obtain 6.2 g of a compound represented by [SPH10]. (Yield: 31%)

MS (MALDI-TOF): m / z = 871.00 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 82.74%; H 4.4%; N, 12.86%

Actual value - C. 82.66%; H 4.46%; N, 12.88%;

Synthesis Example 2 Synthesis of Compound Represented by [SPH34]

(1) Synthesis of Compound Represented by Formula (2-a)

[Chemical Formula 2-a] was synthesized by the following Reaction Scheme 6.

[Reaction Scheme 6]

          [Chemical Formula 1-b] [Chemical Formula 2-a]

27.7 g (0.083 mol) of the compound represented by the above formula (1-b), 30.5 g (0.108 mol) of 3-bromoiodobenzene, 15.8 g (0.249 mol) of copper powder, 18- -6.4 4.4 g (0.017 mol) of potassium carbonate and 57.48 g (0.415 mol) of potassium carbonate were added in this order, 270 ml of ortho-dichlorobenzene was added, and the mixture was refluxed at 180 ° C for 3 days.

When the reaction is complete, extract using 200 ml of methylene chloride and 200 ml of distilled water. Repeat 2 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane alone to remove the ortho-dichlorobenzene. After the solvent was removed, methylene chloride was added in an excess amount to obtain an impure product, which was subjected to column chromatography using methylene chloride: hexane = 1: 20 to obtain 25 g of a compound represented by the formula (2-a). (Yield 64%)

(2) Synthesis of a compound represented by the formula (2-b)

[Chemical Formula 2-b] was synthesized by the following Reaction Scheme 7.

[Reaction Scheme 7]

            [Chemical Formula 2-a] [Chemical Formula 2-b]

25.3 g (0.052 mol) of the compound represented by the formula 2-a, 16.2 g (0.063 mol) of bis (pinacolato) diboron and 1.27 g (0.0016 mol) of PdCl2 (dppf) were placed in a 500- 11.8 g (0.156 mol) of potassium acetate and 250 ml of dimethylsulfoxide were added, and the mixture was refluxed at 110 DEG C for 1 day.

When the reaction is complete, extract using 100 ml of methylene chloride and 500 ml of distilled water. Repeat 3 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using methylene chloride: hexane = 1: 20 to obtain 21.6 g (78%) of the product.

(3) Synthesis of compound represented by [SPH34]

[SPH34] was synthesized according to Reaction Scheme 8 below.

[Reaction Scheme 8]

           [Formula 2-b] [SPH34]

(0.024 mol), chlorodiphenylbenzene 5.1 g (0.019 mol), Pd [PPh3] 4 0.7 g (0.0006 mol), potassium carbonate 8.2 g (0.0588 mol), tetrahydrofuran (50 ml), toluene (50 ml) and water (20 ml), and the mixture was refluxed at 80 ° C for 5 hours.

When the reaction is complete, extract using 50 ml of ethyl acetate and 100 ml of distilled water. Repeat 2 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from methylene chloride and hexane to obtain 3.8 g (29%) of SPH10.

MS (MALDI-TOF): m / z = 639.24 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 84.48%; H 4.57%; N, 10.95%

Actual value - C. 84.26%; H 4.47%; N, 10.83%;

Synthesis Example 3 Synthesis of Compound Represented by [SPH35]

Was synthesized in the same manner as in [Synthesis Example 2], except that 2-chloro-4,6-diphenylpyrimidine was used instead of chlorodiphenylbenzene used in [Reaction Scheme 8] of [Synthesis Example 2] SPH35] was synthesized.

MS (MALDI-TOF): m / z = 638.25 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 84.49%; H 4.73%; N, 8.77%

Actual value - C. 84.26%; H 4.93%; N, 8.74%;

Synthesis Example 4 Synthesis of Compound Represented by [SPH39]

(1) Synthesis of Compound Represented by Formula 4-a

[Formula 4-a] was synthesized by the following Reaction Scheme 9.

[Reaction Scheme 9]

                                                     [Chemical Formula 4-a]

A 5 L round bottom flask was charged with 265 g (0.82 mol) of N-phenyl-3-bromocarbazole and 2500 ml of tetrahydrofuran under a stream of nitrogen. After lowering the temperature to -73 ° C, 670 ml of n-butyllithium was added dropwise. When the dropwise addition was completed, the mixture was stirred at a low temperature for 1 hour, then cooled to room temperature and stirred for 2 hours. The temperature is lowered again to -73 DEG C and 182.5 ml of trimethyl borate is added dropwise. Slowly raise to room temperature, and add 500 ml of 2M hydrochloric acid aqueous solution dropwise. The mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized in hexane to obtain 118 g of a compound represented by the following formula (4-a). (Yield 50%)

(2) Synthesis of Compound Represented by Formula 4-b

[Formula 4-b] was synthesized by the following Reaction Scheme 10.

[Reaction Scheme 10]

         [Formula 4-a] [Formula 4-b]

44.8 g (0.156 mol) of the compound represented by the formula 4-a, 26.26 g (0.13 mol) of 2-bromonitrobenzene, 3.0 g (0.0026 mol) of Pd [PPh3] 4, 45 g (0.325 mol) of potassium, 130 ml of tetrahydrofuran, 130 ml of toluene and 30 ml of water were added, and the mixture was refluxed at 80 ° C for 12 hours.

When the reaction is complete, extract using 200 ml of ethyl acetate and 100 ml of distilled water. Repeat 2 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from methylene chloride and hexane to obtain 40.2 g of a compound represented by the formula (4-b). (Yield: 85%)

(3) Synthesis of Compound Represented by Formula 4-c

[Chemical Formula 4-c] was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

             [Chemical Formula 4-b] [Chemical Formula 4-c]

26.2 g (0.072 mol) of the compound represented by the formula (4-b), 47.14 g (0.18 mol) of triphenylphosphine and 200 ml of dichlorobenzene were added to a 500 ml round bottom flask and refluxed at 160 ° C for 12 hours . When the reaction is completed, it is filtered in a hot state and extracted with methylene chloride and distilled water.

After repeating 2 times, the organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using methylene chloride and hexane to obtain 17.9 g of a compound represented by the following formula 4-c. (Yield: 75%)

(4) Synthesis of Compound Represented by Formula 4-d

[Chemical Formula 4-d] was synthesized by the following Reaction Scheme 12.

[Reaction Scheme 12]

           [Chemical formula 4-c] [Chemical formula 4-d]

13.8 g (0.041 mol) of the compound represented by the formula 4-c, 15.2 g (0.054 mol) of 3-bromoiodobenzene, 7.9 g (0.124 mol) of copper powder, 18- 6 2.2 g (0.008 mol) of potassium carbonate and 28.6 g (0.207 mol) of potassium carbonate were added in this order, 150 ml of ortho-dichlorobenzene was added thereto, and the mixture was refluxed at 180 ° C for 2 days.

When the reaction is complete, extract using 300 ml of methylene chloride and 100 ml of distilled water. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane alone to remove the ortho-dichlorobenzene. After the solvent was removed, methylene chloride was added in an excessive amount to obtain an impure product, which was then subjected to column chromatography with methylene chloride: hexane = 1: 20 to obtain 13 g of a compound represented by the formula 4-d. (Yield 67%)

(5) Synthesis of Compound Represented by Formula 4-e

[Chemical Formula 4-e] was synthesized by the following Reaction Scheme [13].

[Reaction Scheme 13]

           [Chemical Formula 4-d] [Chemical Formula 4-e]

To a 500 mL round bottom flask was added 25.3 g (0.052 mol) of Formula 4-d, 16.2 g (0.063 mol) bis (pinacolato) diboron, 1.27 g (0.0016 mol) PdCl2 (dppf), 11.8 g (0.156 mol) and dimethylsulfoxide (250 ml), and the mixture is refluxed at 110 ° C for 1 day.

When the reaction is complete, extract using 100 ml of methylene chloride and 500 ml of distilled water. Repeat 3 times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using methylene chloride: hexane = 1: 20 to obtain 21.6 g of a compound represented by the following formula (4-e). (Yield: 78%)

(6) Synthesis of compound represented by [SPH39]

[SPH39] was synthesized according to Reaction Scheme 14 below.

[Reaction Scheme 14]

           [Formula 4-e] [SPH39]

13 g (0.028 mol) of the compound represented by the formula 4-e, 5.9 g (0.022 mol) of chlorodiphenyltriazine, 1.02 g (0.0008 mol) of Pd [PPh3] 4, 9.2 g (0.066 mol) of triethylamine, 40 ml of tetrahydrofuran, 40 ml of 1,4-dioxane and 15 ml of water were added, and the mixture was refluxed at 80 ° C for 12 hours.

When the reaction is complete, extract using 100 ml of ethyl acetate and 50 ml of distilled water. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from tetrahydrofuran and hexane to obtain 2.25 g of a compound represented by [SPH39]. (Yield: 16%)

MS (MALDI-TOF): m / z = 639.24 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 84.48%; H 4.57%; N, 10.95%

Actual value - C. 84.16%; H 4.85%; N, 10.99%;

Synthesis Example 5 Synthesis of a compound represented by [SPH75]

Except that 1-chloro-3-diphenylamine-5-phenyltriazine was used in place of chlorodiphenyltriazine used in [Reaction Scheme 14] of <Synthesis Example 4> A compound represented by [SPH75] was synthesized by the same synthetic method.

MS (MALDI-TOF): m / z = 730.28 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 83.81%; H 4.57%; N, 10.95%

Actual value - C. 84.16%; H 4.85%; N, 10.99%;

Examples 1 to 5 Production of an organic electroluminescent device including the compound synthesized by Synthesis Examples 1 to 5

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. DNTPD (700Å) of ITO on the organic material so that after a then attached to a vacuum chamber base pressure was 1 × 10 ^-6 torr substrate, NPD (300Å), the compound + Ir (ppy) ₃ prepared according to the present invention ( Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å).

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

&Lt; Comparative Example 1 &

The organic electroluminescent device for the comparative example was fabricated in the same manner except that CBP of the following structural formula was used in place of the compound prepared by the invention in the device structure of the embodiment.

[CBP]

division Host Dopant Doping concentration (%) ETL V Cd / A COLOR Comparative Example 1 CBP Ir (ppy) ₃ 10 Alq ₃ 7.2 36.24 GREEN Example 1 SPH10 Ir (ppy) ₃ 10 Alq ₃ 3.41 41.74 GREEN Example 2 SPH34 Ir (ppy) ₃ 10 Alq ₃ 3.45 45.46 GREEN Example 3 SPH35 Ir (ppy) ₃ 10 Alq ₃ 3.68 43.13 GREEN Example 4 SPH39 Ir (ppy) ₃ 10 Alq ₃ 3.49 42.21 GREEN Example 5 SPH75 Ir (ppy) ₃ 10 Alq ₃ 3.58 41.96 GREEN

From the results of Examples 1 to 5, Comparative Examples 1 and Table 1, it can be seen that the compound represented by Formula 1 according to the present invention is superior in driving voltage, luminous efficiency And the like can be used effectively for display devices, display devices, lighting, and the like.

Claims (8)

An indolocarbazole derivative represented by the following Chemical Formula 1:
[Chemical Formula 1]

(Wherein,
n is an integer from 1 to 5,
When n is 1, A is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms containing at least one nitrogen,
When n is 2 or more, each A may independently be the same or different and is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, And a heteroaryl group having 3 to 17 carbon atoms, wherein at least one heteroaryl group containing at least one nitrogen must be contained,
Provided that when A is the following structural formula 1,
[Structural formula 1]

The substituent of A is a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, A heteroarylamino group, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 17 carbon atoms. delete delete The method according to claim 1,
An indolecarbazole derivative characterized by being any one compound selected from the group consisting of the following formulas [SPH01] to [SPH99]

[SPH01] [SPH02] [SPH03]

[SPH04] [SPH05] [SPH06]

[SPH07] [SPH08] [SPH09]

[SPH10] [SPH11] [SPH12]

[SPH13] [SPH14] [SPH15]

[SPH16] [SPH17] [SPH18]

[SPH19] [SPH20] [SPH21]

[SPH22] [SPH23] [SPH24]

[SPH25] [SPH26] [SPH27]

[SPH28] [SPH29] [SPH30]

[SPH31] [SPH32] [SPH33]

[SPH34] [SPH35] [SPH36]

[SPH37] [SPH38] [SPH39]

[SPH40] [SPH41] [SPH42]

[SPH43] [SPH44] [SPH45]

[SPH46] [SPH47] [SPH48]

[SPH49] [SPH50] [SPH51]

[SPH52] [SPH53] [SPH54]

[SPH55] [SPH56] [SPH57]

[SPH58] [SPH59] [SPH60]

[SPH61] [SPH62] [SPH63]

[SPH64] [SPH65] [SPH66]

[SPH67] [SPH68] [SPH69]

[SPH70] [SPH71] [SPH72]

[SPH73] [SPH74] [SPH75]

[SPH76] [SPH77] [SPH78]

[SPH79] [SPH80] [SPH81]

[SPH82] [SPH83] [SPH84]

[SPH85] [SPH86] [SPH87]

[SPH88] [SPH89] [SPH90]

[SPH91] [SPH92] [SPH93]

[SPH94] [SPH95] [SPH96]

[SPH97] [SPH98] [SPH99] Anode;
Cathode; And
And a layer containing an indolocarbazole derivative according to claim 1 interposed between the anode and the cathode. 6. The method of claim 5,
Further comprising at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer and an electron blocking layer between the anode and the cathode. The method according to claim 6,
Wherein the indolocarbazole derivative is contained in the light emitting layer between the anode and the cathode. 8. The method of claim 7,
Wherein the thickness of the light emitting layer is 50 to 2,000 ANGSTROM.

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